Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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CROSSLINKABLE POLYMERIC COMPOSITIONS WITH AMINE-
FUNCTIONALIZED INTERPOLYMERS, METHODS FOR
MAKING THE SAME, AND ARTICLES MADE THEREFROM
REFERENCE TO RELATED APPLICATIONS
The present application claims the benefit of U.S. Provisional Application No.
61/992,338, filed on May 13, 2014.
FIELD
Various embodiments of the present invention relate to crosslinkable polymeric
compositions comprising amine-functionalized interpolymers, methods of making
the same, and
articles made therefrom.
INTRODUCTION
Medium, high, and extra-high voltage ("MV," "HV," and "EHV") cables typically
contain a crosslinked polymeric material as an insulation layer, such as a
crosslinked
polyethylene. Such crosslinked polymeric materials can be prepared from a
crosslinkable
polymeric composition having a peroxide initiator. The peroxides used as
initiators for radical
crosslinking in such materials can undergo non-productive decomposition during
storage,
particularly in the presence of an acid, thus reducing the cure potential of
peroxide-containing
crosslinkable compositions. Although advances have been achieved in the field
of crosslinkable
polymeric compositions, improvements are still desired.
SUMMARY
One embodiment is a crosslinkable polymeric composition, comprising:
(a) an ethylene-based polymer;
(b) an organic peroxide; and
(c) an amine-functionalized interpolymer having incorporated therein at
least one
type of amine-containing monomer.
Another embodiment is a crosslinkable polymeric composition, comprising:
(a) an ethylene-based amine-functionalized interpolymer; and
(b) an organic peroxide.
DETAILED DESCRIPTION
Various embodiments of the present invention concern crosslinkable polymeric
compositions comprising an ethylene-based polymer, an organic peroxide, and an
amine-
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functionalized interpolymer. In some embodiments, the ethylene-based polymer
and the amine-
functionalized interpolymer can be present as a single component (i.e., an
ethylene-based amine-
functionalized interpolymer). Additional embodiments concern crosslinked
polymeric
compositions prepared from such crosslinkable polymeric compositions. Further
embodiments
concern coated conductors and processes for producing coated conductors using
the
crosslinkable polymeric compositions.
Crosslinkable Polymeric Composition
As noted above, one component of the crosslinkable polymeric compositions
described
herein is an ethylene-based polymer. As used herein, "ethylene-based" polymers
are polymers
prepared from ethylene monomers as the primary (i.e., greater than 50 weight
percent ("wt%"))
monomer component, though other co-monomers may also be employed. "Polymer"
means a
macromolecular compound prepared by reacting (i.e., polymerizing) monomers of
the same or
different type, and includes homopolymers and interpolymers. "Interpolymer"
means a polymer
prepared by the polymerization of at least two different monomer types. This
generic term
includes copolymers (usually employed to refer to polymers prepared from two
different
monomer types), and polymers prepared from more than two different monomer
types (e.g.,
terpolymers (three different monomer types) and quaterpolymers (four different
monomer
types)).
In various embodiments, the ethylene-based polymer can be an ethylene
homopolymer.
As used herein, "homopolymer" denotes a polymer consisting of repeating units
derived from a
single monomer type, but does not exclude residual amounts of other components
used in
preparing the homopolymer, such as chain transfer agents.
In an embodiment, the ethylene-based polymer can be an ethylene/alpha-olefin
("a-olefin") interpolymer having an a-olefin content of at least 1 wt%, at
least 5 wt%, at least 10
wt%, at least 15 wt%, at least 20 wt%, or at least 25 wt% based on the entire
interpolymer
weight. These interpolymers can have an a-olefin content of less than 50 wt%,
less than 45 wt%,
less than 40 wt%, or less than 35 wt% based on the entire interpolymer weight.
When an a-
olefin is employed, the a-olefin can be a C3_20 (i.e., having 3 to 20 carbon
atoms) linear, branched
or cyclic a-olefin. Examples of C3_20 a-olefins include propene, 1-butene, 4-
methyl- 1-pentene,
1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-
octadecene. The
a-olefins can also have a cyclic structure such as cyclohexane or
cyclopentane, resulting in an a-
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olefin such as 3-cyclohexyl- 1-propene (allyl cyclohexane) and vinyl
cyclohexane. Illustrative
ethylene/a-olefin interpolymers include ethylene/propylene,
ethylene/l-butene,
ethylene/l-hexene, ethylene/l-octene, ethylene/prop ylene/1- octene,
ethylene/prop ylene/1-
butene, and ethylene/1-butene/1-octene.
In various embodiments, the ethylene-based polymer can be used alone or in
combination with one or more other types of ethylene-based polymers (e.g., a
blend of two or
more ethylene-based polymers that differ from one another by monomer
composition and
content, catalytic method of preparation, etc). If a blend of ethylene-based
polymers is
employed, the polymers can be blended by any in-reactor or post-reactor
process.
In various embodiments, the ethylene-based polymer can be selected from the
group
consisting of low-density polyethylene ("LDPE"), linear-low-density
polyethylene ("LLDPE"),
very-low-density polyethylene ("VLDPE"), and combinations of two or more
thereof.
In an embodiment, the ethylene-based polymer can be an LDPE. LDPEs are
generally
highly branched ethylene homopolymers, and can be prepared via high pressure
processes (i.e.,
HP-LDPE). LDPEs suitable for use herein can have a density ranging from 0.91
to 0.94 g/cm3.
In various embodiments, the ethylene-based polymer is a high-pressure LDPE
having a density
of at least 0.915 g/cm3, but less than 0.94 g/cm3, or less than 0.93 g/cm3.
Polymer densities
provided herein are determined according to ASTM International ("ASTM") method
D792.
LDPEs suitable for use herein can have a melt index (I2) of less than 20 g /
10 min., or ranging
from 0.1 to 10 g / 10 min., from 0.5 to 5 g/10min., from 1 to 3 g / 10 min.,
or an 12 of 2 g / 10
min. Melt indices provided herein are determined according to ASTM method
D1238. Unless
otherwise noted, melt indices are determined at 190 C and 2.16 Kg (i.e., 12).
Generally, LDPEs
have a broad molecular weight distribution ("MWD") resulting in a relatively
high polydispersity
index ("PDI;" ratio of weight-average molecular weight to number-average
molecular weight).
In an embodiment, the ethylene-based polymer can be an LLDPE. LLDPEs are
generally ethylene-based polymers having a heterogeneous distribution of
comonomer (e.g., a-
olefin monomer), and are characterized by short-chain branching. For example,
LLDPEs can be
copolymers of ethylene and a-olefin monomers, such as those described above.
LLDPEs
suitable for use herein can have a density ranging from 0.916 to 0.925 g/cm3.
LLDPEs suitable
for use herein can have a melt index (I2) ranging from 1 to 20 g/10min., or
from 3 to 8 g / 10
min.
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In an embodiment, the ethylene-based polymer can be a VLDPE. VLDPEs may also
be
known in the art as ultra-low-density polyethylenes, or ULDPEs. VLDPEs are
generally
ethylene-based polymers having a heterogeneous distribution of comonomer
(e.g., a-olefin
monomer), and are characterized by short-chain branching. For example, VLDPEs
can be
copolymers of ethylene and a-olefin monomers, such as one or more of those a-
olefin monomers
described above. VLDPEs suitable for use herein can have a density ranging
from 0.87 to
0.915 g/cm3. VLDPEs suitable for use herein can have a melt index (I2) ranging
from 0.1 to 20
g/10 min., or from 0.3 to 5 g/10 min.
In an embodiment, the ethylene-based polymer can comprise a combination of any
two
or more of the above-described ethylene-based polymers.
Production processes used for preparing ethylene-based polymers are wide,
varied, and
known in the art. Any conventional or hereafter discovered production process
for producing
ethylene-based polymers having the properties described above may be employed
for preparing
the ethylene-based polymers described herein. In general, polymerization can
be accomplished at
conditions known in the art for Ziegler-Natta or Kaminsky-Sinn type
polymerization reactions,
that is, at temperatures from 0 to 250 C, or 30 or 200 C, and pressures from
atmospheric to
10,000 atmospheres (1,013 megaPascal ("MPa")). In most polymerization
reactions, the molar
ratio of catalyst to polymerizable compounds employed is from 10-12:1 to 10-
1:1, or from 10-9:1
to 10-5:1.
An example of an ethylene-based polymer suitable for use herein is a high-
pressure
low-density polyethylene ("HP-LDPE"), which can have a density of 0.92 g/cc
and a melt index
of 2. Such HP-LDPEs are produced, for example, by The Dow Chemical Company,
Midland,
MI, USA, and can be utilized in commercially available compounds for power
cable insulation.
As noted above, the crosslinkable polymeric compositions described herein
comprise
an organic peroxide. As used herein, "organic peroxide" denotes a peroxide
having the structure:
R1-0-0-R2, or R1 0 0 R 0 0 R2, where each of R1 and R2 is a hydrocarbyl
moiety, and R is a
hydrocarbylene moiety. As used herein, "hydrocarbyl" denotes a univalent group
formed by
removing a hydrogen atom from a hydrocarbon (e.g. ethyl, phenyl) optionally
having one or
more heteroatoms. As used herein, "hydrocarbylene" denotes a divalent group
formed by
removing two hydrogen atoms from a hydrocarbon optionally having one or more
heteroatoms.
The organic peroxide can be any dialkyl, diaryl, dialkaryl, or diaralkyl
peroxide, having the same
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or differing alkyl, aryl, alkaryl, or aralkyl moieties. In an embodiment, each
of R1 and R2 is
independently a C1 to C20 or C1 to C12 alkyl, aryl, alkaryl, or aralkyl
moiety. In an embodiment,
R can be a Ci to C20 or Ci to C12 alkylene, arylene, alkarylene, or aralkylene
moiety. In various
embodiments, R, R1, and R2 can have the same or a different number of carbon
atoms and
structure, or any two of R, R1, and R2 can have the same number of carbon
atoms while the third
has a different number of carbon atoms and structure.
Organic peroxides suitable for use herein include mono-functional peroxides
and di-
functional peroxides. As used herein, "mono-functional peroxides" denote
peroxides having a
single pair of covalently bonded oxygen atoms (e.g., having a structure R-O-O-
R). As used
herein, "di-functional peroxides" denote peroxides having two pairs of
covalently bonded
oxygen atoms (e.g., having a structure R 0 0 R 0 0 R). In an embodiment, the
organic
peroxide is a mono-functional peroxide.
Exemplary organic peroxides include dicumyl peroxide ("DCP"); tert-butyl
peroxybenzoate; di-tert-amyl peroxide ("DTAP"); bis(alpha-t-butyl-
peroxyisopropyl) benzene
("BIPB"); isopropylcumyl t-butyl peroxide; t-butylcumylperoxide; di-t-butyl
peroxide; 2,5-bis(t-
butylperoxy)-2,5-dimethylhexane; 2,5-bis(t-butylperoxy)-2,5-dimethylhexyne-
3; 1,1-bis(t-
butylperoxy)-3,3,5-trimethylcyclohexane; isopropylcumyl cumylperoxide; butyl
4,4-di (tert-
butylperoxy) valerate; di(isopropylcumyl) peroxide; and mixtures of two or
more thereof. In various
embodiments, only a single type of organic peroxide is employed. In an
embodiment, the
organic peroxide is dicumyl peroxide.
As noted above, the crosslinkable polymeric composition further comprises an
amine-
functionalized interpolymer. Such amine-functionalized interpolymers comprise
at least one
type of amine-containing monomer. In various embodiments, the amine-
functionalized
interpolymer can be an interpolymer of one or more olefin-type monomers (e.g.,
a-olefin
monomers) and at least one type of amine-containing monomer. In still other
embodiments, the
amine-functionalized interpolymer and the ethylene-based polymer can be a
single interpolymer
(i.e., an ethylene-based amine-functionalized interpolymer) comprising at
least one type of
amine-containing monomer.
Amine-containing monomers suitable for use in preparing the amine-
functionalized
interpolymer can be any monomer containing an amine group and having at least
one point of
unsaturation. Examples of such monomers include, but are not limited to,
alkenyl amines (e.g.,
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vinylamine, allylamine, etc.) and aminoacrylates. The amine group on the amine-
containing
monomer can be primary, secondary, tertiary, or mixtures thereof. In various
embodiments, the
amine group of the amine-containing monomer can be secondary or tertiary. When
the amine
group of the amine-containing monomer is secondary or tertiary, the
substituents on the amine
group can be hydrocarbyl groups (e.g., alkyl groups) having from 1 to 20
carbon atoms, from 1
to 10 carbon atoms, or from 1 to 6 carbon atoms, and can be branched, cyclic,
or straight-
chained, and saturated or unsaturated. Examples of suitable substituents on
secondary or tertiary
amine groups include, but are not limited to, methyl, ethyl, and t-butyl.
In various embodiments, the amine-containing monomer can be an aminoacrylate.
Examples of suitable aminoacrylates include, but are not limited to, 2-
(diethylamino)ethyl
methacrylate, 2-(dimethylamino)ethyl methacrylate, 2-(t-butylamino)ethyl
methacrylate, and
combinations thereof. In various embodiments, the amine-containing monomer is
selected from
the group consisting of 2-(diethylamino)ethyl methacrylate, 2-
(dimethylamino)ethyl
methacrylate, 2-(t-butylamino)ethyl methacrylate, and mixtures of two or more
thereof.
Alpha-olefin monomers suitable for use in preparing the amine-functionalized
interpolymer can be any a-olefin known or hereafter discovered in the art for
preparing a-olefin-
based polymers. As it pertains to the amine-functionalized interpolymer, the
term "a-olefin"
shall include ethylene. Examples of such monomers include, but are not limited
to, ethylene, or
any C3_20 linear, branched or cyclic a-olefin. Examples of C3_20 a-olefins
include propene,
1-butene, 4-methyl-l-pentene, 1-hexene, 1-o ctene, 1-decene, 1-dodecene, 1-
tetradecene,
1-hexadecene, and 1-octadecene. The a-olefins can also have a cyclic structure
such as
cyclohexane or cyclopentane, resulting in an a-olefin such as 3-cyclohexyl- 1-
propene (allyl
cyclohexane) and vinyl cyclohexane. In various embodiments, the a-olefin
monomer employed
in preparing the amine-functionalized interpolymer is ethylene.
In one or more embodiments, the amine-containing interpolymer is an
ethylene/aminoacrylate copolymer. In further embodiments, the
ethylene/aminoacrylate can
comprise a copolymer of low-density polyethylene either copolymerized or
grafted with an
aminoacryalte monomer, such as those described above (e.g., 2-
(diethylamino)ethyl
methacrylate, 2-(dimethylamino)ethyl methacrylate, 2-(t-butylamino)ethyl
methacrylate, and
mixtures of two or more thereof).
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Preparation of the amine-functionalized interpolymer can be accomplished by
any
known or hereafter discovered methods in the art, including copolymerization
and grafting
techniques. An example of a suitable preparation technique is provided in the
Examples section,
below.
In various embodiments, it is contemplated that the above-described ethylene-
based
polymer and the amine-containing interpolymer can be prepared simultaneously.
For example,
in a reactor where the ethylene-based polymer is being prepared, the amine-
containing monomer
can be fed into the reactor to either copolymerize with a portion of the
monomers used in
preparing the ethylene-based polymer or graft with a portion of formed
ethylene-based polymer.
Thus, in various embodiments, the above-described ethylene-based polymer and
the amine-
containing interpolymer can be a single component (i.e., an ethylene-based
amine-containing
interpolymer). In these embodiments, the crosslinkable polymeric composition
can be a two-
component-based system comprising the ethylene-based amine-functionalized
interpolymer and
an organic peroxide.
The amount of amine-containing monomer employed in preparing the amine-
functionalized interpolymer is not particularly limited and can be varied
according to need. In
various embodiments, however, the amount of amine-containing monomer employed
in
preparing the amine-functionalized interpolymer can range from 0.1 to 20 wt%,
from 0.5 to 10
wt%, from 1 to 5 wt%, or from 1 to 2 wt%, based on the combined weight of all
amine-
containing monomers and olefin-type monomers employed in preparing the amine-
functionalized interpolymer. In embodiments where the ethylene-based polymer
is also the
amine-functionalized interpolymer, the amount of amine-containing monomer
employed can
range from 25 ppm to 2 wt%, or from 25 ppm to 100 ppm, based on the entire
weight of the
ethylene-based amine-functionalized interpolymer.
In various embodiments, the crosslinkable polymeric composition can comprise
the
ethylene-based polymer in an amount ranging from 50 to 99 wt%, from 80 to 99
wt%, from 90 to
99 wt%, or from 95 to 99 wt%, based on the entire crosslinkable polymeric
composition weight.
Additionally, the crosslinkable polymeric composition can comprise the organic
peroxide in an
amount ranging from 0.1 to 5 wt%, from 0.1 to 3 wt%, from 0.4 to 2 wt%, from
0.4 to 1.7 wt%,
from 0.5 to 1.4 wt%, or from 0.7 to less than 1.0 wt%, based on the entire
crosslinkable
polymeric composition weight.
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In various embodiments, the amine-functionalized interpolymer can be present
in the
crosslinkable polymeric composition in an amount sufficient to result in an
amine-
functionalization equivalent in the range of from 25 parts per million ("ppm")
up to
approximately 100 ppm based on the entire weight of the crosslinkable
polymeric composition.
As an example for clarity, an amine-functionalized interpolymer with 2 wt%
aminoacrylate
functionalization, which is utilized in a polymeric composition at 0.5 wt%
would yield (2 wt% x
0.5 wt%) 100 ppm of equivalent amine-functionalization.
Additionally, the amine-functionalized interpolymer can be present in the
crosslinkable
polymeric composition in an amount ranging from 0.1 to 5 wt%, from 0.2 to 2
wt%, or from 0.4
to 0.6 wt%, based on the entire weight of the crosslinkable polymeric
composition. Of course,
the desired concentration of the amine-functionalized interpolymer will vary
depending on the
degree of amine-functionalization in the interpolymer. Amine-functionalized
interpolymers
having low amine content (e.g., 0.1 wt% of the interpolymer) may be used in
higher
concentrations to achieve the desired amine-functionalization equivalent in
the overall
crosslinkable polymer composition. On the other hand, amine-functionalized
interpolymers
having high amine content may be used in lower concentrations.
In other embodiments, when the amine-functionalized interpolymer and the
ethylene-
based polymer are prepared together, the resulting ethylene-based amine-
functionalized
interpolymer can be present in an amount ranging from 1 to 99 wt%, from 50 to
99 wt%, from 80
to 99 wt%, from 90 to 99 wt%, or from 95 to 99 wt%, based on the entire
crosslinkable
polymeric composition weight.
In still other embodiments, based on a molar amine content per gram of
crosslinkable
polymeric composition, the amine-functionalized interpolymer (whether present
as an individual
component or as an ethylene-based amine-functionalized interpolymer) can be
present in an
amount sufficient to yield a molar amine content of 0.1 to 200 micromoles of
amine per gram of
crosslinkable polymeric composition, from 0.1 to 100 micromoles of amine per
gram of
crosslinkable polymeric composition, from 0.1 to 6 micromoles of amine per
gram of
crosslinkable polymeric composition, from 0.2 to 2.5 micromoles of amine per
gram of
crosslinkable polymeric composition, or from 0.5 to 0.7 micromoles of amine
per gram of
crosslinkable polymeric composition.
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In addition to the components described above, the crosslinkable polymeric
composition
may also contain one or more additives including, but not limited to,
antioxidants, crosslinking
coagents, processing aids, fillers, coupling agents, ultraviolet absorbers or
stabilizers, antistatic
agents, nucleating agents, slip agents, plasticizers, lubricants, viscosity
control agents, tackifiers,
anti-blocking agents, surfactants, extender oils, acid scavengers, flame
retardants, and metal
deactivators. Additives, other than fillers, are typically used in amounts
ranging from 0.01 or less
to 10 or more wt% based on total composition weight. Fillers are generally
added in larger
amounts although the amount can range from as low as 0.01 or less to 65 or
more wt% based on
the total composition weight. Illustrative examples of fillers include clays,
precipitated silica and
silicates, fumed silica, calcium carbonate, ground minerals, aluminum
trihydroxide, magnesium
hydroxide, and carbon blacks with typical arithmetic mean particle sizes
larger than 15
nanometers.
In various embodiments, the crosslinkable polymeric composition can comprise
one or
more antioxidants. Exemplary antioxidants include hindered phenols (e.g.,
tetrakis [methylene
(3,5-di-t-buty1-4-hydroxyhydrocinnamate)] methane), less-hindered phenols, and
semi-hindered
phenols; phosphates, phosphites, and phosphonites (e.g., tris (2,4-di-t-
butylphenyl) phosphate);
thio compounds (e.g., distearyl thiodipropionate, dilauryl thiodipropionate);
various siloxanes;
and various amines (e.g., polymerized 2,2,4-trimethy1-1,2-dihydroquinoline).
In various
embodiments, the antioxidant is selected from the group consisting of
distearyl thiodipropionate,
dilauryl thiodipropionate, octadecy1-3,5-di-t-buty1-4-hydroxyhydrocinnamate,
benzenepropanoic
acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy-thiodi-2,1-ethanediy1 ester,
stearyl 3-(3,5-di-t-buty1-
4-hydroxyphenyl) propionate, octadecy1-3-(3,5-di-tert-buty1-4-hydroxypheny1)-
propionate, 2,4-
bis(dodecylthiomethyl)-6-methylphenol, 4,4'-thiobis(6-tert-butyl-m-
cresol), 4,6-
bis(octylthiomethyl)-o-cresol, 1,3 ,5-tris(4-tert-butyl-3-hydroxy-2,6-
dimethyl benz y1)- 1,3,5-
triazine-2,4,6-(1H,3H,5H)-trione, pentaerythritol
tetrakis(3-(3,5-di-t-buty1-4-
hydroxyphenyl)propionate), 2',3-bis [ [343 ,5-di-tert-butyl-4-
hydroxyphenyl] propionyl]]
propionohydrazide, and mixtures of two or more thereof. Antioxidants, when
present, can be
used in amounts ranging from 0.01 to 5 wt%, from 0.01 to 1 wt%, from 0.1 to 5
wt%, from 0.1 to
1 wt%, or from 0.1 to 0.5 wt%, based on the total weight of the crosslinkable
polymeric
composition.
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In various embodiments, the crosslinkable polymeric composition can include
one or
more crosslinking coagents. Examples of such crosslinking coagents include
polyallyl
crosslinking coagents, such as triallyl isocyanurate ("TAIC"), triallyl
cyanurate ("TAC"), triallyl
trimellitate ("TATM"), triallyl orthoformate, pentaerythritol triallyl ether,
triallyl citrate, and
triallyl aconitate; ethoxylated bisphenol A dimethacrylate; cc-methyl styrene
dimer ("AMSD");
acrylate-based coagents, such as trimethylolpropane triacrylate ("TMPTA"),
trimethylolpropane
trimethylacrylate ("TMPTMA"), 1,6-hexanediol diacrylate, pentaerythritol
tetraacrylate,
dipentaerythritol pentaacrylate, tris(2-hydroxyethyl) isocyanurate
triacrylate, and propoxylated
glyceryl triacrylate; vinyl-based coagents, such as polybutadiene having a
high 1,2-vinyl content,
and trivinyl cyclohexane ("TVCH"); and other coagents as described in USP
5,346,961 and
4,018,852. When employed, the crosslinkable polymeric composition can comprise
the
crosslinking coagent(s) in an amount ranging from 0 to 3 wt%, from 0.1 to 3
wt%, from 0.5 to 3
wt%, from 0.7 to 3 wt%, from 1.0 to 3 wt%, or from 1.5 to 3 wt%, based on the
entire
crosslinkable polymeric composition weight.
In various embodiments, the crosslinkable polymeric composition can comprise
at least
one component that is acidic or that has one or more acidic decomposition
products. As mentioned
above and discussed in more detail below, it is believed that acidic species
in the crosslinkable
polymeric composition contribute to degradation of the organic peroxide, and
thus loss of cure
potential, via acid-catalyzed decomposition. Peroxide degradation in this
manner does not result in
the radicals that initiate polymer crosslinking and thus result in loss of
cure potential. The source
of the acidic component can vary greatly and is not particularly limited.
However, in various
embodiments, the source of the acidic component can be any one or more of the
additives
described above, such as antioxidants, crosslinking coagents, and processing
aids, among others.
For example, acidic species can be generated by the oxidation of common
stabilizers to yield, for
example, sulfur-based, phosphorous-based, or carboxylic acids. In various
embodiments, the
source of the acidic component can be an antioxidant. In still further
embodiments, the source of
the acidic component is distearyl dithiopropionate.
Preparation of Crosslinkable Polymeric Composition
Preparation of the cross-linkable polymeric composition can comprise
compounding
the above-described components. For example, compounding can be performed by
either (1)
compounding all components into the ethylene-based polymer, or (2) compounding
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components except for the organic peroxide, which can be soaked in as
described below.
Compounding of the cross-linkable polymeric composition can be effected by
standard
equipment known to those skilled in the art. Examples of compounding equipment
are internal
batch mixers, such as a BrabenderTm, BanburyTM, or BollingTM mixer.
Alternatively, continuous
single or twin screw, mixers can be used, such as a FanelTM continuous mixer,
a Werner and
PfleidererTM twin screw mixer, or a BussTM kneading continuous extruder.
Compounding can be
performed at a temperature of greater than the melting temperature of the
ethylene-based
polymer up to a temperature above which the ethylene-based polymer begins to
degrade. In
various embodiments, compounding can be performed at a temperature ranging
from 100 to
200 C, or from 110 to 150 C.
Alternatively, in one or more embodiments, the ethylene-based polymer and any
optional components can first be melt compounded according to the above-
described procedure
and pelletized. The amine-functionalized interpolymer can then be added to the
pellets, mixed at
elevated temperature (e.g., 130 C), then pressed, cooled, and cut into strips
to be extruded at
elevated temperature (e.g., 200 C) and pelletized again. Next, the organic
peroxide and the
cross-linking coagent, if employed, can be soaked into the resulting ethylene-
based polymer
compound, either simultaneously or sequentially. In an embodiment, the organic
peroxide and
optional coagent can be premixed at the temperature above the melting
temperature of the
organic peroxide and optional coagent, whichever is greater, followed by
soaking the ethylene-
based polymer compound in the resulting mixture of the organic peroxide and
optional cross-
linking coagent at a temperature ranging from 30 to 100 C, from 50 to 90 C,
or from 60 to
80 C, for a period of time ranging from 1 to 168 hours, from 1 to 24 hours,
or from 3 to 12
hours.
The resulting crosslinkable polymeric composition can have increased
resistance to loss
of cure potential. Though not wishing to be bound by theory, it is believed
that the amine
functionality imparted to the crosslinkable polymeric composition by the amine-
functionalized
interpolymer improves retention of the cure potential of the crosslinkable
polymeric
composition. Essentially, it is believed that the amine functionality inhibits
or interferes with the
acid-catalyzed decomposition of the peroxide in the crosslinkable polymeric
composition, thus
preserving cure potential.
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In one or more embodiments, the crosslinkable polymeric composition has an
initial cure
potential (CP0) when crosslinked immediately upon preparation of the
crosslinkable polymeric
composition, as described in the following Examples, and measured as maximum
torque (in-lbs) by
moving die rheometer at 182 C. Additionally, the crosslinkable polymeric
composition has a heat-
aged cure potential CP14 when crosslinked after aging the crosslinkable
polymeric composition at
70 C and ambient pressure for 14 days, as described in the following
Examples, and measured as
maximum torque (in-lbs) by moving die rheometer at 182 C. In various
embodiments, the
crosslinkable polymeric composition has a ratio of CP14 to CP0 of at least
0.1, at least 0.2, at least 0.3,
at least 0.4, at least 0.5, at least 0.6, at least 0.7, at least 0.8, or at
least 0.9, and up to 1.1, or 1.
In one or more embodiments, the crosslinkable polymeric composition has heat-
aged cure
potential CP21 when crosslinked after aging the crosslinkable polymeric
composition at 70 C and
ambient pressure for 21 days, as described in the following Examples, and
measured as maximum
torque (in-lbs) by moving die rheometer at 182 C. In various embodiments, the
crosslinkable
polymeric composition has a ratio of CP21 to CP0 of at least 0.1, at least
0.2, at least 0.3, at least 0.4,
at least 0.5, at least 0.6, at least 0.7, at least 0.8, or at least 0.9, and
up to 1.1, or 1.
Crosslinked Polymeric Composition
The above-described crosslinkable polymeric composition can be cured or
allowed to
cure in order to form a crosslinked ethylene-based polymer. Such curing can be
performed by
subjecting the crosslinkable polymeric composition to elevated temperatures in
a heated cure
zone, which can be maintained at a temperature in the range of 175 to 260 C.
The heated cure
zone can be heated by pressurized steam or inductively heated by pressurized
nitrogen gas.
Thereafter, the crosslinked polymeric composition can be cooled (e.g., to
ambient temperature).
The crosslinking process can create volatile decomposition byproducts in the
crosslinked polymeric composition. The term "volatile decomposition products"
denotes
byproducts formed during the curing step, and possibly during the cooling
step, by initiation of
the organic peroxide. Such byproducts can comprise alkanes, such as methane.
Following
crosslinking, the crosslinked polymeric composition can undergo degassing to
remove at least a
portion of the volatile decomposition byproducts. Degassing can be performed
at a degassing
temperature, a degassing pressure, and for a degassing time period to produce
a degassed
polymeric composition. In various embodiments, the degassing temperature can
range from 50
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to 150 C, or from 60 to 80 C. In an embodiment, the degassing temperature is
65 to 75 C.
Degassing can be conducted under standard atmosphere pressure (i.e., 101,325
Pa).
Coated Conductor
A cable comprising a conductor and an insulation layer can be prepared
employing the
above-described crosslinkable polymeric composition. "Cable" and "power cable"
mean at least
one wire or optical fiber within a sheath, e.g., an insulation covering and/or
a protective outer
jacket. Typically, a cable is two or more wires or optical fibers bound
together, usually in a
common insulation covering and/or protective jacket. The individual wires or
fibers inside the
sheath may be bare, covered or insulated. Combination cables may contain both
electrical wires
and optical fibers. Typical cable designs are illustrated in USP 5,246,783,
6,496,629 and
6,714,707. "Conductor" denotes one or more wire(s) or fiber(s) for conducting
heat, light,
and/or electricity. The conductor may be a single-wire/fiber or a multi-
wire/fiber and may be in
strand form or in tubular form. Non-limiting examples of suitable conductors
include metals
such as silver, gold, copper, carbon, and aluminum. The conductor may also be
optical fiber
made from either glass or plastic.
Such a cable can be prepared with various types of extruders (e.g., single or
twin screw
types) by extruding the crosslinkable polymeric composition onto the
conductor, either directly
or onto an interceding layer. A description of a conventional extruder can be
found in
USP 4,857,600. An example of co-extrusion and an extruder therefore can be
found in
USP 5,575,965.
Following extrusion, the extruded cable can pass into a heated cure zone
downstream of
the extrusion die to aid in crosslinking the crosslinkable polymeric
composition and thereby
produce a crosslinked polymeric composition. The heated cure zone can be
maintained at a
temperature in the range of 175 to 260 C. In an embodiment, the heated cure
zone is a
continuous vulcanization ("CV") tube. In various embodiments, the crosslinked
polymeric
composition can then be cooled and degassed, as discussed above.
Alternating current cables can be prepared according to the present
disclosure, which
can be low voltage, medium voltage, high voltage, or extra-high voltage
cables. Further, direct
current cables can be prepared according to the present disclosure, which can
include high or
extra-high voltage cables.
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TEST METHODS
Moving Die Rheometer
Perform moving die rheometer ("MDR") testing at 182 C respectively according
to the
methods described in ASTM D5289 on an Alpha Technologies MDR 2000. The cure
potential is
determined using an MDR, which applies an oscillatory strain on a molten
sample held at
182 C, while recording the torque. As the compound crosslinks, the torque
increases to reach a
steady torque maximum, Mh. The comparison of Mh as a function of thermal aging
time (at
70 C, for example) provides a means to compare the composition's ability to
retain cure
potential over long storage times under near-ambient conditions.
Heat Aging
Samples are heat aged in jars sealed with MYLARTM film under screw-on cap
within a
laboratory oven at 70 C. Just enough material is removed from the jar after
specified aging time
for MDR testing, after which the jar is re-sealed and returned to the oven for
further heat aging.
Preparation of Crosslinked Plaque Sample for Dissipation Factor Test
A sufficient amount of pelleted compound is compression molded to fill an
8"x8"x0.010" frame. Compression molding is conducted using the following
sequence of
conditions: i) 3 minutes at 125 C and 125 psi, ii) 5 minutes at 125 C and
2500 psi, iii) quench-
cool, iv) remove excess flashing, cut into pieces, and continue with
additional press-protocol, v)
3 minutes at 125 C and 500 psi, vi) 3 minutes at 125 C and 2500 psi, vii)
increase temperature
to 182 C and hold 12 minutes at 2500 psi, viii) quench cool.
Dissipation Factor
The 60-Hz dissipation factor is measured on 3-inch discs cut from crosslinked
plaques
of samples at a temperature of 120 C and an electrical stress of 25 kV/mm.
This is performed
by inserting the sample between the flat circular electrodes of a Soken sample
holder/test cell
Model DAC-OBE-7. The test cell is filled with oil, using Galden D03 Perfluoro
Polyether from
Solvay Specialty Polymers, which is heated and circulated using a temperature-
controlled oil
bath. Measurements are taken 1 hour after the sample is inserted to ensure
that the system is in
thermal equilibrium at the target test temperature. A power supply is used to
provide up to 60
Hz 10 kV test voltage. A Soken Automatic Schering Bridge Model DAC-PSC-UA is
utilized to
measure the dissipation factor with a Soken Model DAC-Cs-102A 1000 pF
reference capacitor.
Density
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Determine density according to ASTM D792.
Melt Index
Measure melt index, or 12, in accordance with ASTM D1238, condition 190 C /
2.16 kg,
and report in grams eluted per 10 minutes.
MATERIALS
The following materials are employed in the Examples, below.
The low-density polyethylene ("LDPE") employed has a melt index (I2) of 2 g/10
min., a
density of 0.920 g/cm3, and is produced by The Dow Chemical Company, Midland,
MI, USA.
2-(dimethylamino)ethyl methacrylate is commercially available from Sigma
Aldrich, St.
Louis, MO, USA.
2-(diethylamino)ethyl methacrylate is commercially available from Sigma
Aldrich, St.
Louis, MO, USA.
2-(t-butylamino)ethyl methacrylate is commercially available from Sigma
Aldrich, St.
Louis, MO, USA.
Propionaldehyde (97%) is commercially available from Sigma Aldrich, St. Louis,
MO,
USA.
Tert-butyl peroxyacetate (50% by weight solution in isododecane) is
commercially
available from Fisher Scientific, Pittsburgh PA, USA.
n-Heptane is commercially available from Sigma Aldrich, St. Louis, MO, USA.
Ethylene monomer is commercially available from Praxair.
Distearyl thiodipropionate ("DSTDP;" antioxidant) is commercially available
from
Reagens, S.p.A, Bologna, Italy.
Cyanox TM 1790 (tris[(4-tert-buty1-3-hydroxy-2,6-
dimethylphenyl)methy1]-1,3,5-
triazinane-2,4,6-trione; antioxidant) is commercially available from Cytec
Industries, Woodland
Park, NJ, USA.
Dicumyl peroxide is commercially available from Arkema Inc.
EXAMPLES
Example 1
Prepare a control ethylene polymer and three ethylene/aminoacrylate copolymers
according to the following method.
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Undiluted aminoacrylate monomer (either 2-(dimethylamino)ethyl methacrylate, 2-
(diethylamino)ethyl methacrylate, or 2-(t-butylamino)ethyl methacrylate) is
loaded into a 0.25-L
glass supply vessel, which is open to the atmosphere. As the chain transfer
agent, a fresh
250-mL bottle of undiluted propionaldehyde (97%) is used as the supply vessel,
which is open to
the atmosphere. As the initiator, tert-butyl peroxyacetate (2.3 grams of a 50%
by weight
solution in isododecane) is combined with 500 mL of n-heptane and loaded into
a third glass
supply vessel. This solution is purged with nitrogen to minimize dissolved
oxygen.
For the control sample, inject ethylene at 1,000 gm/hr (35.65 moles/hr), at a
pressure of
2,000 bar, into an agitated (2,000 rpm) 54-mL high-pressure continuous stirred
tank reactor
("CSTR"), with an external heating jacket set at 187 C. Next, degas the
propionaldehyde by an
HPLC degasser and then add to the ethylene stream at a pressure of 250 bar and
a rate of 3.46
gm/hr (60 millimoles/hr). Then the mixture is compressed to 2,000 bar. The
peroxide initiator is
added to the ethylene-propionaldehyde mixture at a pressure of 2,000 bar and a
rate of 3.2 x 10-3
gm/hr (0.024 millimoles/hr) before the mixture enters the reactor.
The ethylene conversion to polymer is 10.5 wt% based on the mass of ethylene
entering
the reactor, and the average reaction temperature is 220 C. An ethylene-based
polymer having a
melt index (12) of 4.5 g/10 min. is obtained. Approximately 70 grams of
ethylene-based polymer
is collected.
For the ethylene/aminoacrylate samples, undiluted aminoacrylate monomer is
pumped at
a pressure of 250 bar and a rate of 1.84 gm/hr (11.7 millimoles/hr) through an
HPLC degasser,
and then into the propionaldehyde stream, and mixed before the mixture is
added to the ethylene
stream and compressed to 2,000 bar. The peroxide initiator is added to the
ethylene-
propionaldehyde-aminoacrylate mixture at a pressure of 2,000 bar and a rate of
4.6 x 10-3 gm/hr
(0.036 millimoles/hr), before the mixture enters the reactor.
The ethylene conversion to polymer is 11 wt% based on the mass of ethylene
entering the
reactor, and the average reaction temperature is 218 C. An ethylene-based
polymer having a
melt index (12) of 5 g/10 min is obtained. Approximately 350 grams of
ethylene/aminoacrylate
polymer is collected.
The comparison above illustrates the method of sample preparation of an
ethylene-based
amine-functionalized interpolymer useful in the present invention; the
addition of the
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aminoacrylate has little impact on the ethylene conversion or melt index of
the resulting
polymer.
The following ethylene/aminoacrylate copolymers are obtained according to the
above-
described procedure:
Table 1 ¨ Ethylene/Aminoacrylate Copolymer Properties
Sample Aminoacrylate Type
Aminoacrylate content (wt %)
Designation
A 2-(diethylamino)ethyl methacrylate 1.98 wt%
2-(dimethylamino)ethyl methacrylate 1.66 wt%
2-(t-butylamino)ethyl methacrylate 1.30 wt%
Example 2
Prepare one comparative sample ("CS1") and three samples ("S1-S3") according
to the
formulations listed in Table 2, below.
Table 2¨ Compositions of CS1 and S1-S3
Component (wt%) CS1 Si S2 S3
LDPE 99.63 99.13 99.13 99.13
DSTDP 0.23 0.23 0.23 0.23
CyanoxTM 1790 0.14 0.14 0.14 0.14
Ethylene/aminoacrylate "A" 0.5
Ethylene/aminoacrylate "B" 0.5
Ethylene/aminoacrylate "C" 0.5
Preblend Total: 100 100 100 100
Peroxide Soak:
Preblend (wt%) 98.2 98.2 98.2 98.2
Dicumyl Peroxide (wt%) 1.8 1.8 1.8 1.8
Aminoacrylate Content:
Aminoacrylate content in 0 100 100 85
composition (ppm)
Approximate micromoles of 0 0.58 0.58 0.59
amine groups per gram of
composition
The sample formulations shown in Table 2 are prepared according to the
following
procedure. The LDPE, DSTDP and Cyanox 1790 are melt compounded together in a
Werner
Pfleiderer twin-screw extruder (Model ZSK-30) and then pelletized. A Brabender
mixing bowl
is then used at 130 C and 30 rpm to flux the stabilized LDPE. For the samples
Sl-S3, the
ethylene/aminoacrylate copolymer is added to the mixer, and the mixing process
is continued for
an additional 5 minutes. The resulting compositions are pressed, cooled, and
cut into strips to
feed into a single-screw extruder. Extrusion is performed at 200 C melt
temperature to form
strands that can be pelletized into approximately 1/8" diameter pellets.
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Next, the dicumyl peroxide is soaked into the samples as follows. First, 100 g
of pellets
of the preblend are pre-heated in an oven for 4 hours at 70 C in 8-oz. glass
jars. Molten dicumyl
peroxide (-55 C) is added to the jars. The jars are sealed with a MYLARTM
film under the
screw-on lid, and tumbled, returned to the oven for approximately 15 minutes,
then tumbled or
shaken again to ensure that the pellet surface is dry (indicating the peroxide
has been absorbed).
The pellets are then allowed to soak overnight in the oven at 70 C.
Samples are removed from the jar to evaluate the cure potential as a function
of thermal
aging time. The samples are heat aged and their cure potential is determined
using a Moving Die
Rheometer (MDR) according to the procedures described above. Results of these
analyses are
provided in Table 3, below.
Table 3¨ Heat-Aged Cure Potential Retention of CS1 and S1-S3
(values listed represent Mh in in-lbs)
Days at 70 C CS1 Si S2 S3
0 3.19 3.17 3.19
2.66
4 3.25 3.36 3.25
2.66
7 2.66 3.36 3.39
2.72
13 0.16 3.39 3.28
2.73
21 (0.16)* 3.48 3.36
2.75
28 (0.16)* 3.47 2.53
2.69
CP13/CP0** 0.05 >1 >1 >1
CP21/CP0 0.05 >1 >1 >1
*(inferred value based upon earlier cure measurements, for use in calculation
of cure ratio CP,JCP0)
**Note that CP13/CP0 is used as a reasonable approximation to CP14/CP0
As seen in Table 3, CS1 is found to lose its cure potential between 7 and 13
days of
thermal aging at 70 C, which is characteristic of the acid-catalyzed
decomposition of the
peroxide. However, for Sl-S3, the addition of a small amount of amine
functionality through the
ethylene/aminoacrylate copolymer results in cure potential retention for over
4 weeks. This is a
clear indication that the amine functionality within the copolymer is
mitigating the acid-
catalyzed decomposition of the peroxide.
Example 3
Prepare each of CS1 and Sl-S3 for determining dissipation factor according to
the
following procedure. Each of the samples prepared as described in Example 2 is
pressed into a
12-mil plaque and crosslinked as described above. The resulting plaques are
stored in a vacuum
oven at 60 C for 4 days to remove volatile byproducts from the crosslinking
reaction. 3-inch
disks are cut from the plaques and analyzed for dissipation factor according
to the above-
described Test Methods. Results are provided in Table 4, below.
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Table 4¨ Dissipation Factor of CS1 and S1-S3
CS1 Si S2 S3
DF at 120 C and 25 kV/mm <0.1 % <0.1 % <0.1 %
<0.1%
In all cases, the samples have a dissipation factor of less than 0.1 percent.
This indicates
that each one is suitable for use as insulation in high-voltage AC power
cables.
Example 4
Prepare three additional Samples (S4-S6) by using a portion of the preblend of
CS1
(containing no peroxide) to dilute the preblends of 51 and S2. Perform this
dilution on a 2-roll
mill (0.4-mm gap, 20 rpm, approximate mix time of 6 minutes, roll temperature
of 115 C,
during which material is cut from the edges and fed into the center of the
roll approximately 10
times) to achieve the formulations in Table 5.
Table 5 ¨ Compositions of S4-S6
Component (wt%) S4 S5 S6
Preblend of CS1 50 75 50
Preblend of Si 50 25
Preblend of S2 50
Preblend Total: 100 100 100
Peroxide Soak:
Preblend (wt%) 98.2 98.2 98.2
Dicumyl Peroxide (wt%) 1.8 1.8 1.8
Aminoacrylate Content:
Aminoacrylate content in 50 25 50
composition (ppm)
Approximate micromoles 0.29 0.15 0.29
of amine groups per gram
of compound
Milled sheets are then diced into small squares about 0.5 cm in size, and 50 g
of the
diluted and diced material is inserted into a 16-oz. jar. The dicumyl peroxide
is soaked into the
samples in a similar fashion as described in Example 2. First, the 50 g of
each diced material is
pre-heated in an oven for 4 hours at 70 C in 16-oz. glass jars. Molten
dicumyl peroxide
(-55 C) is added to the jars. The jars are sealed with a MylarTM film under
the screw-on lid, and
tumbled, returned to the oven for approximately 15 minutes, then tumbled or
shaken again to
ensure that material surface is dry (indicating the peroxide has been
absorbed). The material is
then allowed to soak overnight in the oven at 70 C.
Samples are removed from the jar to evaluate the cure potential as a function
of thermal
aging time. The samples are heat aged and their cure potential is determined
using a Moving Die
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Rheometer (MDR) according to the procedures described above. Results of these
analyses are
provided in Table 6, below.
Table 6- Heat-Aged Cure Potential Retention of S4-S6
(values listed represent Mh in in-lbs)
Days of Aging at 70 C S4 S5 S6
0 (2.66)* 2.50 2.66
4 2.66 2.54 2.65
7 2.63 2.56 2.66
14 2.56 2.56 2.70
21 1.46 2.59 2.70
28 0.25 2.49 2.07
CP14/CP0 0.96 >1 >1
CP21/CP0 0.55 >1 >1
(* inferred based upon 4-day measurement... actual value not measured).
The magnitude of the initial cure potential for the diluted samples is
noticeably lower
than that of CS1 and S1-S3. This reduction in initial cure potential is most
likely the result of the
increased surface area of the larger 16-oz. jar leading to a reduced
efficiency of incorporation of
peroxide into the flat squares as compared to the pelletized material. Despite
this reduction in
initial cure potential, an excellent retention of cure potential, as
represented by the ratio of
CP14/CP0, has been maintained for all of the dilution samples.
Example 5
Prepare one comparative sample ("CS2") and three samples ("S7-S9") according
to the
formulations listed in Table 7, below.
Table 7- Compositions of CS2 and S7-S9
Component (wt%) S7 S8 S9
CS2
LDPE 99.13 99.38 99.5
99.63
DSTDP 0.23 0.23 0.23
0.23
CyanoxTM 1790 0.14 0.14 0.14
0.14
Ethylene/aminoacrylate "A" 0.5 0.25 0.13 0
Preblend Total: 100 100 100
100
Peroxide Soak:
Preblend (wt%) 98.2 98.2 98.2
98.2
Dicumyl Peroxide (wt%) 1.8 1.8 1.8
1.8
Aminoacrylate Content:
Aminoacrylate content in 100 50 25 0
composition (ppm)
Approximate micromoles of 0.58 0.29 0.15 0
amine groups per gram of
composition
The sample formulations shown in Table 7 are prepared according to the
following
procedure. The LDPE, DSTDP and Cyanox 1790 are melt compounded together in a
Brabender
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mixing bowl at 130 C and 30 rpm, by first melting the LDPE and then adding
the antioxidants,
and mixing for 1 minute. The aminoacrylate copolymer is added to the melt in
the Brabender
mixing bowl and mixing is continued for 5 minutes at 130 C and 30 rpm. The
resulting
compositions are pressed, cooled, and cut into strips to feed into a single-
screw extruder.
Extrusion is performed at 200 C melt temperature to form strands that can be
pelletized into
approximately 1/8" diameter pellets.
Next, the dicumyl peroxide is soaked into the samples as follows. First, 100 g
of pellets
of the preblend are pre-heated in an oven for 4 hours at 70 C in 8-oz. glass
jars. Molten dicumyl
peroxide (-55 C) is added to the jars. The jars are sealed with a MylarTM
film under the screw-
on lid, and tumbled, returned to the oven for approximately 15 minutes, then
tumbled or shaken
again to ensure that the pellet surface is dry (indicating the peroxide has
been absorbed). The
pellets are then allowed to soak overnight in the oven at 70 C.
Samples are removed from the jar to evaluate the cure potential as a function
of thermal
aging time. The samples are heat aged and their cure potential is determined
using a Moving Die
Rheometer (MDR) according to the procedures described above. Results of these
analyses are
provided in Table 8, below.
Table 8¨ Heat-Aged Cure Potential Retention of CS2 and S7-S9
(values listed represent Mh in in-lbs)
Days at 70 C S7 S8 S9 CS2
0 3.12 3.28 3.23 3.30
4 3.23 3.30 3.21 3.21
7 3.23 3.33 3.20 3.26
14 3.24 3.37 3.24 1.87
21 3.25 3.44 1.86 0.17
28 3.25 2.47 0.17 0.17
CP14/CP0 >1 >1 >1 0.57
CP21/CP0 >1 >1 0.58 0.05
The revised dilution scheme of samples S7-S9 and C52, more similar to the
preparation
of samples CS1 and Sl-S3, yields a more reproducible initial torque (as
compared to Table 3).
Here, a consistent trend has been established in the effectiveness of the
amine functionality to
preserve the cure potential of the composition. The retention of the cure
potential based upon 14
days of heat aging has been maintained with as little as 25 ppm of amino
acrylate or an equivalent
of 0.15 micromoles of amine.
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